CN117509629A - Edge fluorinated nano graphene material and preparation method and application thereof - Google Patents

Abstract

The invention discloses an edge fluorinated nanographene material and its preparation method and application. This edge-fluorinated nanographene material uses decachlorocentrocene as the starting material and is prepared by a new bottom-up synthesis strategy combined with fluorine atom pre-installation through Suzuki‑Miyaura coupling reaction and Scholl reaction; This preparation method successfully overcomes the problem of no selectivity caused by the violent reactivity of the fluorination reaction. It not only maintains the π conjugated system of nanographene intact, but also achieves precise polyfluorination or even perfluorination of its edges. Edge fluorinated nanographene materials, especially edge perfluorinated nanographene, exhibit high electron affinity, low molecular orbital energy levels, high electron mobility, good solubility, thermal stability, and conductivity. and biocompatibility, with potential applications in organic light-emitting diodes, organic photovoltaic cells, organic field-effect transistors, bioimaging/biomedicine and other fields.

Description

An edge fluorinated nanographene material and its preparation method and application

Technical field

The invention relates to the technical field of semiconductor materials, and in particular to an edge fluorinated nanographene material and its preparation method and application.

Background technique

Fluorinated nanographene material is a nanocarbon material that introduces fluorine atoms into the interior or edge of graphene sheets with a size between 1 and 100nm. Due to the introduction of fluorine atoms, the physical, chemical and photoelectric properties of fluorinated nanographene have been greatly improved compared to before fluorination, which makes it useful in the fields of organic semiconductors, electrode materials, high-stability materials and new biomedical materials. has broad application prospects.

The traditional method for preparing fluorinated nanographene materials is direct fluorination. Due to the violent reactivity of the fluorination reaction, the π-conjugated system of the product produced by this method is often destroyed, and the original electrical conductivity, thermal conductivity, photophysical and electrochemical properties of graphene are no longer available. . Moreover, since the direct fluorination method does not have regional selectivity and the location and quantity of the fluorination reaction are uncontrollable, the types of products prepared are complex and it is difficult to obtain a single product. As a result, its structure-activity relationship cannot be studied in depth, making its application difficult. Development has also been severely restricted.

Contents of the invention

In order to solve the above problems, the present invention breaks away from the limitations of the traditional fluorination method and provides an edge polyfluorinated or perfluorinated nanographene with a clear structure through a new bottom-up synthesis strategy of pre-installation of fluorine atoms. Novel preparation method of materials. The present invention realizes fluorination only at the edge of nanographene. While completely retaining the π-conjugated system of the graphene core, through controllable fluorination quantity and position, a product with a clear structure was obtained, and its properties and applications in the fields of organic semiconductors and biomedicine were explored. .

The present invention adopts the following technical solutions:

An edge fluorinated nanographene material, the edge fluorinated nanographene material uses nanographene as the core, and the hydrogen atoms at the edge of the core are replaced by a certain number of fluorine atoms, and the number of fluorine atom substitutions is 10-30; The chemical structural formula of the edge fluorinated nanographene material is as follows:

Wherein, when R ₁ and R ₂ are fluorine atoms and hydrogen atoms respectively, the molecular formula of the edge fluorinated nanographene material is C ₈₀ H ₂₀ F ₁₀ ; when R ₁ and R ₂ are hydrogen atoms and fluorine atoms respectively, The molecular formula of the edge fluorinated nanographene material is C ₈₀ H ₁₀ F ₂₀ ;

When R ₁ and R ₂ are both fluorine atoms, there are two bonding modes of the edge fluorinated nanographene material, namely complete cyclization and incomplete cyclization. When complete cyclization, the dotted line Bonding is formed, and the molecular formula of the edge fluorinated nanographene material is C ₈₀ F ₃₀ ; when there is incomplete cyclization, no bonding is formed at the dotted line, and the molecular formula of the edge fluorinated nanographene material is C ₈₀ H ₆ F ₃₀ .

Preferably, all the cores are six-membered rings, or contain non-six-membered ring defects, and the non-six-membered rings are five-membered rings, seven-membered rings, or eight-membered rings; when all are six-membered rings, the entirety of the core The spatial structure is planar; when it contains non-six-membered ring defects, the overall spatial structure of the core is curved, and its structural fragments include any of the following:

Preferably, when the core contains 1 five-membered ring and 5 seven-membered ring defects, and a total of 10 fluorine atoms are substituted at the edges, R ₁ is a fluorine atom and R ₂ is a hydrogen atom, that is, the edge fluorinated nanoparticles The molecular formula of graphene material is C ₈₀ H ₂₀ F ₁₀ , and its chemical structural formula is:

Preferably, when the core contains 1 five-membered ring and 5 seven-membered ring defects, a total of 30 fluorine atoms are substituted on the edges, and the benzene substituent is completely cyclized, R ₁ and R ₂ are both fluorine atoms, that is, the The molecular formula of edge fluorinated nanographene material is C ₈₀ F ₃₀ , and its chemical structural formula is:

Preferably, when the core contains 1 five-membered ring and 5 seven-membered ring defects, a total of 30 fluorine atoms are substituted on the edges, and the benzene substituent is not completely cyclized, R ₁ and R ₂ are both fluorine atoms, that is, the The molecular formula of the edge fluorinated nanographene material is C ₈₀ H ₆ F ₃₀ , and its chemical structural formula is:

A method for preparing edge fluorinated nanographene materials, specifically including the following steps:

S1. Decachlorocentrocene and 4-fluorophenylboronic acid achieve ten-fold Suzuki-Miyaura coupling under the action of palladium catalyst to obtain deca(4-fluorophenyl)centrocene;

S2. Perform intramolecular dehydrogenation cyclization of deca(4-fluorophenyl)carboxene in step S1 through Scholl reaction, and purify the mixture through RP-HPLC to obtain edge decafluoro-substituted edge fluorinated nanographene. Material C ₈₀ H ₂₀ F ₁₀ .

A method for preparing edge fluorinated nanographene materials, specifically including the following steps:

S1. Suzuki-Miyaura coupling of decachlorocentrocene and 3,4,5-trifluorophenylboronic acid is achieved under the action of palladium catalyst to obtain deca(3,4,5-trifluorophenyl)trifluorophenylboron;

S2. Perform intramolecular dehydrogenation cyclization of deca(3,4,5-trifluorophenyl)carboxene in step S1 through Scholl reaction, and purify the mixture through RP-HPLC to obtain a complete ring with perfluorinated edges. The edge fluorinated nanographene material C ₈₀ F ₃₀ .

A method for preparing edge fluorinated nanographene materials, specifically including the following steps:

S1. Suzuki-Miyaura coupling of decachlorocentrocene and 3,4,5-trifluorophenylboronic acid is achieved under the action of palladium catalyst to obtain deca(3,4,5-trifluorophenyl)trifluorophenylboron;

S2. Perform intramolecular dehydrogenation cyclization of deca(3,4,5-trifluorophenyl)carboxene in step S1 through Scholl reaction, and purify the mixture through silica gel column chromatography to obtain edge polyfluorinated unsubstituted Completely cyclized edge fluorinated nanographene material C ₈₀ H ₆ F ₃₀ .

Preferably, the base used in the Suzuki-Miyaura coupling reaction is potassium phosphate; the organic solvent used in the Suzuki-Miyaura coupling reaction is toluene; the oxidizing agent used in the Scholl reaction is 2,3-dichloro-5, 6-dicyanobenzoquinone; the organic acid used in the Scholl reaction is trifluoromethanesulfonic acid; the organic solvent used in the Scholl reaction is methylene chloride.

An application of edge fluorinated nanographene material, which is used as an n-type semiconductor in organic field effect transistors, organic light emitting diodes and organic photovoltaic cells; the edge fluorinated nanographene As a heat-resistant material, the graphene material is suitable for lubricant additives in high-temperature, high-speed and high-pressure environments; the edge-fluorinated nanographene material is suitable for biological imaging and biomedicine as a bio-friendly material.

After adopting the above technical solution, compared with the background technology, the present invention has the following advantages:

1. The present invention realizes polyfluorination or even perfluorination at the edges of nanographene, and completely retains the π conjugated structure and properties of the core of nanographene, providing a basis for the precise synthesis of more peripheral polyfluorinated nanographenes. New strategies and ideas.

2. The product of the present invention can be separated and purified by conventional means, and its structure can be clearly characterized by high-resolution mass spectrometry, hydrogen nuclear magnetic resonance spectroscopy, carbon spectrum, fluorine spectrum, and X-ray single crystal diffraction. Therefore, it can be combined with its optical properties. , electrical and other properties to conduct in-depth study of its structure-activity relationship.

3. The material of the present invention has a special chiral saddle-shaped topology, and due to the strong electronegativity of fluorine atoms and the substitution of edge fluorine atoms, which reduces the intermolecular force, compared to the unmodified saddle-shaped topology, C ₈₀ H ₃₀ , C ₈₀ F ₃₀ and C ₈₀ H ₆ F ₃₀ etc. have better solubility, higher fluorescence quantum yield and lower highest occupied orbital (HOMO) energy level and lowest unoccupied orbital (LUMO) energy class. Thanks to the intact retention of the π conjugated structure, the electron transport performance is good (Figure 8), and due to edge fluorination, it has high electron affinity. Therefore, this fluorinated nanographene material can serve as a potential electron acceptor. The materials are used in devices such as organic light-emitting diodes OFETs, organic field-effect transistors OLEDs, or organic photovoltaic cells OPV.

4. As the fluorine content of the present invention increases, the high bond energy of C-F bonds significantly improves the thermal stability of nanographene. Among them, the thermogravimetric analysis curve of the edge perfluorinated product shows a sharp weight loss between 600 and 700°C, with the maximum slope at 635°C. This dissociation temperature is about 90°C higher than that of nanographene before fluorination. In addition, the dissociation temperature of the decafluoride product is also significantly higher than before fluorination (Figure 9). This shows that the edge-fluorinated nanographene material has higher thermal stability and can be used as a potential heat-resistant material in the fields of catalysis, lubrication and semiconductors. They can withstand high temperatures, corrosive and oxidizing environments, extending the life and reliability of the device or equipment.

5. Incubate HeLa cells with dimethyl sulfoxide (DMSO) solutions of two types of polyfluorinated nanographene prepared in the present invention at 37°C for 24 hours or 48 hours (Figure 10). The results show that deca- and perfluorinated nanographene has almost no toxicity up to 200 μM, indicating that edge-fluorinated nanographene has good in vitro biocompatibility and can be used in biomonitoring and biomedicine fields.

Description of drawings

Figure 1 is a high-resolution mass spectrum of the edge decafluorinated nanographene material prepared in Example 1 of the present invention;

Figure 2 is a ¹ H NMR spectrum of the edge decafluorinated nanographene material prepared in Example 1 of the present invention;

Figure 3 is a high-resolution mass spectrum of the edge perfluorinated nanographene material prepared in Example 2 of the present invention;

Figure 4 is a ¹⁹ FNMR chart of the edge perfluorinated nanographene material prepared in Example 2 of the present invention;

Figure 5 is a ¹³ C{ ¹⁹ F} NMR chart of the edge perfluorinated nanographene material prepared in Example 2 of the present invention;

Figure 6 is a high-resolution mass spectrum of edge polyfluorinated nanographene prepared in Example 3 of the present invention;

Figure 7 is a ¹³ C{ ¹⁹ F} NMR chart of the edge polyfluorinated nanographene material prepared in Example 3 of the present invention;

Figure 8 is a comparison chart of the electron mobility of the edge perfluorinated nanographene material prepared in Example 2 of the present invention and PCBM;

Figure 9 is a thermogravimetric analysis curve of the edge perfluorinated nanographene material prepared in Example 2 of the present invention;

Figure 10 shows the cytotoxicity experimental results of edge polyfluorinated nanographene materials prepared in Examples 1 and 2 of the present invention.

Detailed ways

In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention and are not intended to limit the present invention. The test methods described in the following examples, unless otherwise specified, are all conventional methods; the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial sources.

See Figures 1 to 10.

Embodiment 1

The structural formula of the edge decafluorinated nanographene material (C ₈₀ H ₂₀ F ₁₀ ) in this embodiment is:

The synthesis route is as follows:

(1) Combine decachlorocentrocene (119 mg, 0.2 mmol), 4-fluorophenylboronic acid (839 mg, 6 mmol), Pd(PPh ₃ ) ₄ (277 mg, 0.2 mol) and K ₃ PO ₄ (1.48 g, 7 mmol). ) was added to a 50mL two-necked round-bottomed flask, and filled with _N2 three times. Then 10 mL of degassed toluene, 10 mL of degassed _H2O and 5 mL of degassed 1,4-dioxane were added to the mixture. The mixture was then stirred at 100°C for 7 days. After the mixture was cooled to room temperature, the mixture was extracted with dichloromethane (DCM) and washed three times with water. The DCM layer was collected and concentrated, and then the crude product was purified by silica gel column chromatography, eluting with hexane:dichloromethane (v:v)=2:1 to obtain the deca(4-fluorophenyl)yl core ring in the form of a yellow powder. Alkene (yield 61%). ¹ H NMR (400MHz, CDCl ₃ , 298K) δ6.51 (dd, J (F, H) = 12Hz, 20H), 6.30 (t, J (F, H) = 16Hz, 20H). ¹³ C NMR (100MHz , CDCl ₃ ,298K)δ162.16-159.71(d,J(C,F)＝245Hz),142.21,135.00(d,J(C,F)＝4Hz),133.12(d,J(C,F) ＝8Hz),132.06,127.77,113.56(d,J(C,F)＝21Hz).HRMS(Maldi-TOF-MS)m/z calcd for C ₈₀ H ₄₀ F ₁₀ [M] ^- :1189.289, found: 1189.873.

(2) Synthesis of edge decafluorinated nanographene material (C ₈₀ H ₂₀ F ₁₀ ):

Deca(4-fluorobenzene)ylcyclocene (119 mg, 0.1 mmol) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 681 mg, 3 mmol) were added to 25 mL Double-necked flask and filled with _N2 three times. Then 10 mL of dry dichloromethane (DCM) and 1.5 mL of trifluoromethanesulfonic acid (TfOH) were added to the mixture. The mixture was then stirred at room temperature for 30 minutes. Then 10 mL of saturated _NaHCO solution was added to the mixture to quench the reaction. The mixture was extracted with DCM and washed 3 times with water. The organic phase was collected and evaporated, and then the crude product was separated by silica gel column chromatography, eluting with hexane:dichloromethane=2:1 (v:v) to obtain edge decafluorinated nanographene and some incomplete dehydrogenation. _{Mixture of} cyclized _by -products (identified by MS as _C80H22F10 and _{C80H24F10 )} . The mixture was further purified by RP-HPLC to obtain edge decafluorinated nanographene material (C ₈₀ H ₂₀ F ₁₀ ) with a yield of 9.6%. ¹ H NMR (400MHz, 1,1,2,2-tetrachloroethane-d ₂ ,363K) δ8.09-8.07(d,J(F,H)＝8Hz,10H),7.30-7.28(d,J(F ,H)＝8Hz,10H).HRMS(Maldi-TOF-MS)m/zcalcd forC ₈₀ H ₂₀ F ₁₀ [M] ^- :1170.140, found:1170.132.

Table 1 X-ray crystallographic data of the edge decafluorinated nanographene material (C ₈₀ H ₂₀ F ₁₀ ) prepared in Example 1

Embodiment 2

The structural formula of the edge perfluorinated nanographene material (C ₈₀ F ₃₀ ) in this embodiment is:

The synthesis route is as follows:

(1) Combine decachlorocentrocene (119mg, 0.2mmol), 3,4,5-trifluorophenylboronic acid (1.06g, 6mmol), Pd(PPh ₃ ) ₄ (277mg, 0.2mol) and K ₃ PO ₄ (1.48g, 7mmol) was added to a 50mL two-necked round-bottomed flask, and filled with _N2 three times. Then 10 mL of degassed toluene, 10 mL of degassed _H2O and 5 mL of degassed 1,4-dioxane were added to the mixture. The mixture was then stirred at 100°C for 7 days. After the mixture was cooled to room temperature, the mixture was extracted with dichloromethane (DCM) and washed three times with water. The DCM layer was collected and concentrated, and then the crude product was purified by silica gel column chromatography, eluting with hexane:dichloromethane (v:v)=2:1 to obtain deca(3,4,5-fluorobenzene in the form of a yellow powder) ) base ring ene (yield 58%). ¹ H NMR (400MHz, CD ₂ Cl ₂ , 298K) δ 6.43 (t, J (F, H) = 12 Hz, 20H). ¹³ C NMR (100 MHz, CD ₂ Cl ₂ , 298K) δ 151.63-149.18 ( d,J(C,F)＝245Hz),140.45,134.14,133.04,127.18,116.26(d,J(C,F)＝6Hz),116.11(d,J(C,F)＝6Hz).HRMS( Maldi-TOF-MS)m/z calcd for C ₈₀ H ₂₀ F ₃₀ [M] ^- :1549.100, found:1549.414.

(2) Synthesis of edge perfluorinated nanographene material (C ₈₀ F ₃₀ ):

Deca(3,4,5-trifluorobenzene)ylcyclocene (133 mg, 0.086 mmol) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 780.9 mg , 3.44mmol) was added to a 25mL double-necked flask, and _N2 was charged three times. Then 10 mL of dry dichloromethane (DCM) and 3 mL of trifluoromethanesulfonic acid (TfOH) were added to the mixture. The mixture was then stirred at room temperature for 90 minutes. Then 10 mL of saturated _NaHCO solution was added to the mixture to quench the reaction. The mixture was extracted with DCM and washed 3 times with water. The organic phase was collected and evaporated, and then the crude product was separated by silica gel column chromatography, eluting with hexane:dichloromethane=40:1 (v:v) to obtain edge perfluorinated nanographene materials and some incompletely desorbed nanographene materials. A mixture of _by -products _{of the} hydrocyclization ( _the other two products were identified by MS as _C80H2F30 and _C80H4F30 ). The mixture was further purified by RP-HPLC to obtain edge-perfluorinated C ₈₀ F ₃₀ nanographene material in 6% yield. ¹³ C{ ¹⁹ F} NMR (150MHz, CD ₂ Cl ₄ ,298K) δ175.57,151.57,151.54,150.18,149.72,149.66,149.64,149.30,149.24,149.14,149.04,148.83,148.78,1 47.97,147.93,147.87,146.91 ,140.83,140.71,140.57,140.45,140.28,140.03,139.87,139.78,138.67,138.61,137.00,136.98,136.49,136.44,133.99,133.64,133.40,132 .72,132.38,132.31,131.64,131.51,131.33,131.31,131.19 ,131.05,130.91,130.79,130.73,130.42,130.33,130.24,130.20,129.80,129.71,129.61,129.28,129.18,129.14,128.82,128.76,127.80,116 .32,116.25,113.47,113.45,113.36,113.02,112.92,112.36 ,112.15,112.09,111.92,111.84,111.64,111.29,111.21,111.18,110.76,110.65,110.59,110.21,109.98. ¹⁹ F NMR (565MHz, CD ₂ Cl ₄ ,298K) δ-121. 29(d,J(F, F)＝24Hz,1F),-121.68(d,J(F,F)＝18Hz,1F),-121.85(t,J(F,F)＝24Hz,1F),-121.96(t,J(F) ,F)＝30Hz,1F),-122.15(t,J(F,F)＝30Hz,1F),-122.77(t,J(F,F)＝30Hz,1F),-123.04(t,J( F,F)＝30Hz,1F),-123.04(t,J(F,F)＝30Hz,1F),-126.04(t,J(F,F)＝30Hz,1F),-126.90(dd,J (F,F)＝60Hz,1F),-127.40(t,J(F,F)＝30Hz,1F),-127.45(t,J(F,F)＝30Hz,1F),-127.86(dd, J(F,F)＝60Hz,1F),-129.13(dd,J(F,F)＝60Hz,1F),-129.44(dd,J(F,F)＝60Hz,1F),-129.63(t ,J(F,F)＝24Hz,1F),-129.97(d,J(F,F)＝6Hz,1F),-130.19(dd,J(F,F)＝48Hz,1F),-130.34( dd,J(F,F)＝48Hz,1F),-134.31(t,J(F,F)＝42Hz,1F),-153.76(t,J(F,F)＝60Hz,1F),-153.87 (t,J(F,F)＝60Hz,1F),-153.92(t,J(F,F)＝60Hz,1F),-154.60(t,J(F,F)＝60Hz,1F),- 155.08(t,J(F,F)＝60Hz,1F),-155.67(t,J(F,F)＝42Hz,2F),-155.97(t,J(F,F)＝48Hz,1F), -155.74(m,J(F,F)＝78Hz,2F).HRMS(Maldi-TOF-MS)m/z calcd forC ₈₀ F ₃₀ [M] ^- :1529.952, found:1529.952.

Table 2 X-ray crystallographic data table of edge perfluorinated nanographene (C ₈₀ F ₃₀ ) prepared in Example 2;

Embodiment 3

The structural formula of the edge polyfluorinated nanographene material (C ₈₀ H ₆ F ₃₀ ) in this embodiment is:

The synthesis route is as follows:

(1) Combine decachlorocentrocene (119mg, 0.2mmol), 3,4,5-trifluorophenylboronic acid (1.06g, 6mmol), Pd(PPh ₃ ) ₄ (277mg, 0.2mol) and K ₃ PO ₄ (1.48g, 7mmol) was added to a 50mL two-necked round-bottomed flask, and filled with _N2 three times. Then 10 mL of degassed toluene, 10 mL of degassed _H2O and 5 mL of degassed 1,4-dioxane were added to the mixture. The mixture was then stirred at 100°C for 7 days. After the mixture was cooled to room temperature, the mixture was extracted with dichloromethane (DCM) and washed three times with water. The DCM layer was collected and concentrated, and then the crude product was purified by silica gel column chromatography, eluting with hexane:dichloromethane (v:v)=2:1 to obtain deca(3,4,5-fluorobenzene in the form of a yellow powder) ) base ring ene (yield 58%). ¹ H NMR (400MHz, CD ₂ Cl ₂ , 298K) δ 6.43 (t, J (F, H) = 12 Hz, 20H). ¹³ C NMR (100 MHz, CD ₂ Cl ₂ , 298K) δ 151.63-149.18 ( d,J(C,F)＝245Hz),140.45,134.14,133.04,127.18,116.26(d,J(C,F)＝6Hz),116.11(d,J(C,F)＝6Hz).HRMS( Maldi-TOF-MS)m/z calcd for C ₈₀ H ₂₀ F ₃₀ [M] ^- :1549.100, found:1549.414.

(2) Synthesis of polyfluorinated nanographene material (C ₈₀ H ₆ F ₃₀ ):

Deca(3,4,5-trifluorobenzene)ylcyclocene (133 mg, 0.086 mmol) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 780.9 mg , 3.44mmol) was added to a 25mL double-necked flask, and _N2 was charged three times. Then 10 mL of dry dichloromethane (DCM) and 3 mL of trifluoromethanesulfonic acid (TfOH) were added to the mixture. The mixture was then stirred at room temperature for 90 minutes. Then 10 mL of saturated _NaHCO solution was added to the mixture to quench the reaction. The mixture was extracted with DCM and washed 3 times with water. The organic phase is collected and evaporated, and then the crude product is separated by silica gel column chromatography, eluting with hexane:dichloromethane=40:1 (v:v) to obtain polyfluorinated nanographene material C ₈₀ H ₆ F ₃₀ , the yield is 24%. C ₈₀ H ₆ F ₃₀ : ¹³ C{ ¹⁹ F } NMR (CDCl ₃ , 25°C, 125MHz) δ 151.305-111.000 (80C); HRMS (MALDI-TOF-MS): C ₈₀ H ₆ F ₃₀ [M ^· ] ⁺ Theoretical value is 1536.001, and the detection value is 1535.592.

The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person familiar with the technical field can easily think of changes or modifications within the technical scope disclosed in the present invention. All substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (10)

1. An edge fluorinated nanographene material, characterized in that: the edge fluorinated nano graphene material takes nano graphene as an inner core, hydrogen atoms at the edge of the inner core are replaced by a certain number of fluorine atoms, and the number of the replaced fluorine atoms is 10-30; the chemical structural formula of the edge fluorinated nano graphene material is as follows:

wherein R is ₁ And R is ₂ When the fluorine atoms and the hydrogen atoms are respectively adopted, the molecular formula of the edge fluorinated nano graphene material is C ₈₀ H ₂₀ F ₁₀ ；R ₁ And R is ₂ When the fluorine atoms are hydrogen atoms and fluorine atoms respectively, the molecular formula of the edge fluorinated nano graphene material is C ₈₀ H ₁₀ F ₂₀ ；

When R is ₁ And R is ₂ When the two are fluorine atoms, the bonding modes of the edge fluorinated nano graphene material are respectively complete cyclization and incomplete cyclization, wherein when the two are completely cyclized, a bond is formed at a dotted line, and the molecular formula of the edge fluorinated nano graphene material is C ₈₀ F ₃₀ The method comprises the steps of carrying out a first treatment on the surface of the When the cyclisation is incomplete, no bond is formed at the dotted line, and the molecular formula of the edge fluorinated nano graphene material is C ₈₀ H ₆ F ₃₀ 。

2. An edge-fluorinated nanographene material according to claim 1, characterized in that: the inner core is all six-membered rings or contains defects of non-six-membered rings, wherein the non-six-membered rings are five-membered rings, seven-membered rings or eight-membered rings; when all the cores are six-membered rings, the whole space structure of the inner core is a plane; when the core contains non-six-membered ring defects, the whole space structure of the core is bent, and the structural fragment comprises any one of the following components:

3. an edge-fluorinated nanographene material according to claim 2, characterized in that: when the inner core contains 1 five-membered ring and 5 seven-membered ring defects, the edges replace 10 fluorine atoms altogether, R ₁ Is a fluorine atom, R ₂ Is a hydrogen atom, namely the molecular formula of the edge fluorinated nano graphene material is C ₈₀ H ₂₀ F ₁₀ To be converted intoThe chemical structural formula is as follows:

4. an edge-fluorinated nanographene material according to claim 2, characterized in that: when the inner core contains 1 five-membered ring and 5 seven-membered ring defects, the edges are substituted with 30 fluorine atoms altogether, and the benzene substituent is completely cyclized, R ₁ And R is ₂ Are all fluorine atoms, namely the molecular formula of the edge fluorinated nano graphene material is C ₈₀ F ₃₀ The chemical structural formula is as follows:

5. an edge-fluorinated nanographene material according to claim 2, characterized in that: when the inner core contains 1 five-membered ring and 5 seven-membered ring defects, the edges are substituted with 30 fluorine atoms altogether, and the benzene substituent is incompletely cyclized, R ₁ And R is ₂ Are all fluorine atoms, namely the molecular formula of the edge fluorinated nano graphene material is C ₈₀ H ₆ F ₃₀ The chemical structural formula is as follows:

6. a method for preparing the edge fluorinated nano graphene material according to claim 3, comprising the following steps:

s1, realizing the coupling of ten-weight Suzuki-Miyaura under the action of a palladium catalyst by using decachlorocycloalkene and 4-fluorobenzeneboronic acid to obtain ten (4-fluorophenyl) cycloalkene;

s2, passing the ten (4-fluorophenyl) endocyclic alkene in the step S1Carrying out intramolecular dehydrocyclization reaction by Scholl reaction, purifying the mixture by RP-HPLC to obtain the edge decafluoro-substituted edge fluorinated nano graphene material C ₈₀ H ₂₀ F ₁₀ 。

7. A method for preparing the edge fluorinated nano graphene material according to claim 4, comprising the following steps:

s1, realizing Suzuki-Miyaura coupling of decachlorocycloalkene and 3,4, 5-trifluorophenylboronic acid under the action of a palladium catalyst to obtain deca (3, 4, 5-trifluorophenyl) cycloalkene;

s2, carrying out intramolecular dehydrocyclization reaction on the ten (3, 4, 5-trifluoro phenyl) endocyclic alkene in the step S1 through Scholl reaction, and purifying the mixture through RP-HPLC to obtain the edge perfluorinated completely cyclized edge fluorinated nano graphene material C ₈₀ F ₃₀ 。

8. A method for preparing the edge fluorinated nano graphene material according to claim 5, comprising the following steps:

s1, realizing Suzuki-Miyaura coupling of decachlorocycloalkene and 3,4, 5-trifluorophenylboronic acid under the action of a palladium catalyst to obtain deca (3, 4, 5-trifluorophenyl) cycloalkene;

s2, carrying out intramolecular dehydrocyclization reaction on the ten (3, 4, 5-trifluoro phenyl) endocyclic alkene in the step S1 through Scholl reaction, and purifying the mixture through silica gel column chromatography to obtain the edge polyfluoro-substituted incompletely cyclized edge fluorinated nano graphene material C ₈₀ H ₆ F ₃₀ 。

9. A method for preparing an edge fluorinated nanographene material according to any one of claims 6 to 8, wherein: the alkali adopted in the Suzuki-Miyaura coupling reaction is potassium phosphate; the organic solvent adopted in the Suzuki-Miyaura coupling reaction is toluene; the oxidant used in the Scholl reaction is 2, 3-dichloro-5, 6-dicyano-p-benzoquinone; the organic acid used in the Scholl reaction is trifluoromethanesulfonic acid; the organic solvent used in the Scholl reaction is methylene dichloride.

10. Use of the edge-fluorinated nanographene material according to claim 1, characterized in that: the edge fluorinated nano graphene material is applied to an organic field effect transistor, an organic light emitting diode and an organic photovoltaic cell as an n-type semiconductor; the edge fluorinated nano graphene material is used as a heat-resistant material and is suitable for a lubricant additive in high-temperature, high-speed and high-pressure environments; the edge fluorinated nano graphene material is suitable for biological imaging and biomedicine as a biological friendly material.